CN106693997B - A kind of diesel hydrogenation for removal sulphur catalyst and its preparation method and application - Google Patents

A kind of diesel hydrogenation for removal sulphur catalyst and its preparation method and application Download PDF

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CN106693997B
CN106693997B CN201710015431.9A CN201710015431A CN106693997B CN 106693997 B CN106693997 B CN 106693997B CN 201710015431 A CN201710015431 A CN 201710015431A CN 106693997 B CN106693997 B CN 106693997B
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catalyst
preparation
heteropoly acid
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CN106693997A (en
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卢玉坤
梁吉雷
柳云骐
刘晨光
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China University of Petroleum East China
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China University of Petroleum East China
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of diesel hydrogenation for removal sulphur catalyst and its preparation method and application, and preparation method includes the preparation of (1) metal heteropoly acid presoma, to H3PMo12O40Suitable Ba (OH) is added in solution2It neutralizes it just and obtains Ba3/2PMo12O40Solution, then to Ba3/2PMo12O40The sulfate of a certain amount of promoter metal is added in solution, the BaSO that will be generated in solution4Precipitating is filtered to remove；A certain amount of ammonium salt heteropoly acid presoma is added in filtrate, filters (NH4)3PMo12O40, which is evaporated to obtain crude product metal heteropoly acid presoma, suitable metal heteropoly acid presoma is configured to the maceration extract of various concentration by the preparation of (2) catalyst precursor, is impregnated in carrier γ-Al using equi-volume impregnating2O3On；(3) catalyst precursor is placed in presulfurization in tube furnace.The application is prepared the metal salt of heteropoly acid by the method for ion exchange by the ammonium salt of heteropoly acid by ion exchange, and with good hydrodesulfurization reaction performance, conversion ratio and the hydrogenolysis selectivity of sulfide are higher.

Description

A kind of diesel hydrogenation for removal sulphur catalyst and its preparation method and application
Technical field
The present invention is a kind of preparation method and applications of diesel oil hydrogenation catalyst, in particular to one kind is using heteropoly acid as oxygen The diesel hydrogenation for removal sulphur catalyst and its preparation method and application of compound presoma.
Background technique
The a large amount of exhaust emissions of car ownership rapid growth bring have become the main reason for haze weather occurs it One, there are strict requirements in various countries for sulfur content in automotive oils, and European Union just proposed the Europe V of automotive oils early in 2009 Standard, i.e. Sulfur Content in Petroleum Products are not higher than 10 μ g/g.State IV petrol and diesel oil standard (sulfur content≤50 were implemented in full in 2015 in China μ g/g), implementation state V petrol and diesel oil standard (sulfur content≤10 μ g/g) in 2017.The standard in six stages is also being formulated, it is contemplated that 2016 The end of the year completes, and according to the situation demands that current environment is protected, six standard of state can further add the row of tight nitrogen oxides and particulate matter Limit value is put, overall goal is to add tight 30% in five standard base of state.It is continuously increased and environmental law in this motor vehicle fuel demand It advises under increasingly strict dual-pressure, China's Oil Refining Industry faces huge challenge.Currently, industrial petrol and diesel oil desulfurization mainly uses and adds The method of hydrogen, and most crucial in the links of hydroprocessing is hydrogenation catalyst.Therefore, one for cracking above-mentioned problem The minimum method of cost effectiveness is to develop the Hydrobon catalyst of high activity.
The activity of HDS catalyst depends primarily on its composition and preparation method, especially active phase precursor.Currently, big Partial HDS catalyst mainly uses two kinds of preparation methods: direct sulphided state method or oxidation state vulcanization.The former mainly uses heat The suitable metal sulfide of solution, such as four thio ammonium molybdate and the sulfo-amino salt of Ni containing auxiliary agent (Co) etc..However, this side There is also some larger disadvantages for method, for example, used metal sulfide is more toxic；And its preparation is complicated, production process In can generate a large amount of noxious materials, seriously pollute environment；These disadvantages also limit the large-scale industrial application of this method.Separately A kind of outer method is that the maceration extract containing oxidation state metal component is carried on carrier, is roasted, vulcanization.This method is in industry On be widely applied, and the MoS containing auxiliary agent Ni (Co) of alumina load2Catalyst is presently most used one kind. Currently, this kind of routine maceration extract is mainly prepared by ammonium molybdate, nickel nitrate etc., in this, as the presoma of catalyst activity phase.
MoS containing auxiliary agent Ni (Co)2Catalyst is containing there are two types of " Co (Ni)-Mo-S " active phases: I type " Co (Ni)-Mo- S " activity phase and II type " Co (Ni)-Mo-S " active phase.The former incomplete vulcanization and stacking number of plies is few, and the latter's complete cure and The stacking number of plies is more.Also, the activity of II type " Co (Ni)-Mo-S " activity phase will be much higher than I type " Co (Ni)-Mo-S " active phase, This is because I type " Co (Ni)-Mo-S " activity is met through Mo-O-Al bridged bond and alumina catalyst support there are stronger active force, It is unfavorable for caused by the dispersion of active phase.Therefore, in terms of this angle, the activity of Yao Tigao HDS catalyst then needs to increase II type The content of " Co (Ni)-Mo-S " activity phase, this requires Mo and Ni (Co) auxiliary agent atom be as far as possible in catalyst preparation process Contact it is close, Ni (Co) auxiliary agent atom and Mo contact tightness degree can also be used as measure Ni (Co) promoter effect a kind of mark It is quasi-.
Summary of the invention
Based on considerations above, we replace routine using a kind of compound simultaneously containing Mo and Ni or Co auxiliary agent atom Ammonium molybdate, nickel nitrate etc. are that active phase precursor prepares HDS catalyst, and nickel molybdenum heteropolyacid cluster molecule has contains Mo and Ni simultaneously The advantage of auxiliary agent atom may be used as the HDS catalyst of new active phase precursor preparation high activity.The thiophene of these catalyst Pheno, dibenzothiophenes (DBT), the HDS activity rating tables of data of the compounds such as 4,6- dimethyl Dibenzothiophenes (4,6-DMDBT) Bright, the catalyst of the more conventional precursor preparation of reactivity is high.
The present invention is to be realized by the following technical programs, a kind of preparation method of Hydrobon catalyst, including Following steps:
(1) preparation of metal heteropoly acid presoma
To H3PMo12O40Suitable Ba (OH) is added in solution2It neutralizes it just and obtains Ba3/2PMo12O40Solution, then Compare according to metering to Ba3/2PMo12O40The sulfate of a certain amount of promoter metal is added in solution, the BaSO that will be generated in solution4It is heavy Shallow lake is filtered to remove；A certain amount of ammonium salt heteropoly acid presoma is added according to stoichiometric ratio in filtrate, which is added Heat is cooled to room temperature to 40~100 DEG C and after continuing 1~5h of stirring, filters (NH4)3PMo12O40, which is evaporated to obtain thick Resultant metal heteropoly acid presoma, is finally recrystallized；
(2) preparation of catalyst precursor
Suitable metal heteropoly acid presoma is configured to the maceration extract of various concentration, is soaked using equi-volume impregnating Stain is in carrier γ-Al2O3On, dry 2h is put into 120 DEG C of baking ovens；
(3) catalyst precursor is placed in presulfurization in tube furnace.
It is further preferred that ammonium salt heteropoly acid presoma described in step (1) is (NH4)4[(HPO3)2Mo5O15]、(NH4)6 [P2Mo18O62]、(NH4)4[NiMo6O24H6One of].
It is further preferred that the sulfate that step (1) is added is CoSO4Or NiSO4；The metal heteropoly acid presoma is The cobalt salt or nickel salt of heteropoly acid.
It is further preferred that (the NH4)4[(HPO3)2Mo5O15] the preparation method comprises the following steps: it is soluble in water using phosphorous acid, so After a certain amount of ammonium hydroxide is added, solution is heated to boiling；It is a small amount of into solution that MoO is repeatedly added3, filtered after powder dissolution；Filter Liquid boils evaporation and is allowed to volume concentration to certain volume, then cools to room temperature；Powdered crystal is collected by filtration, using 10mL ice Water is dried in air to get (NH after repeatedly washing4)4[(HPO3)2Mo5O15] ammonium salt heteropoly acid.
It is further preferred that the phosphorous acid: ammonium hydroxide: MoO3Between molar ratio be 1:1~3.1:1.5~4.
It is further preferred that the filtrate, which boils evaporation, is allowed to volume concentration to 15-20mL.
The present invention also protects prepared by the above method using Ni (Co) MoS as the multicomponent catalyst of active component.
It is further preferred that mass fraction of the catalyst containing active component is 5-20%, with MoO3Content calculates.
The present invention also protects application of the above-mentioned catalyst in diesel hydrogenation for removal sulphur.
The present invention provides a kind of diesel hydrogenation for removal sulphur catalyst and its preparation method and application, the catalyst is to contain Ni (Co) Strandberg structure heteropoly acid M2[(HPO3)2Mo5O15] it is oxide precursor, γ-Al2O3For carrier, nickel-loaded (cobalt) molybdenum sulphur [Ni (Mo) MoS] active component, obtained catalyst have good dispersibility, and catalyst preparation temperature is low, Method is simple, easy, and II type " Co (Ni)-Mo-S " activity phase number is more, is remarkably improved the activity and selectivity of catalyst.
Compared with prior art, the present invention using biggish (NH can be generated in conventional precursor preparation catalyst process4)4 [Ni(OH)6Mo6O18] particle, reunite, hence it is evident that the pore structure of blocking catalyst is unfavorable for the progress of catalysis reaction.In contrast, Ni and Mo exists together in a molecule in the nickel molybdenum heteropolyacid cluster of the application preparation, closely coupled between atom, can be to avoid above-mentioned Side reaction occurs, so the catalyst nickel molybdenum component particle of preparation is small, dispersed more preferable.HRTEM and DRIFT characterization result table It is bright, the II type Ni-Mo-S activity phase of high activity in the HDS catalyst based on Strandberg structure nickel molybdenum heteropolyacid cluster presoma Quantity it is more, catalyst activity is high.
The HDS reaction network of DBT is as shown in figure 8, the DBT primary product that HDS reacts on a catalyst is biphenyl (BP), ring Hexyl benzene (CHB) and its isomers, in addition there are also a small amount of partial hydrogenation products, such as tetrahydro dibenzothiophenes (4H-DBT) and six Diphenyl hydrogen bithiophene (6H-DBT), micro full hydrogenation products bigeminy hexamethylene (BCH) and its isomers.The HDS of DBT reacts master To pass through two parallel response paths: one is direct hydrogenolysis path (DDS), i.e. C-S key in DBT is broken generation first BP, BP partial hydrogenation generate CHB and its isomers cyclopentyl-phenyl methane, and partial hydrogenation product generates again after further adding hydrogen Perhydro product BCH and its isomers cyclopenta-cyclohexyl-methane；Another is to add hydrogen path (HYD), i.e. one in DBT Phenyl ring part is first hydrogenated to 4H-DBT and 6H-DBT, and then the fracture of C-S key generates CHB, and final CHB isomerization generates ring penta Base-phenylmethane, or further hydro-conversion is perhydro product BCH and its isomers cyclopenta-cyclohexyl-methane.But CHB adds The amount and BP of hydrogen generation BCH and its isomers are hydrogenated to amount all very littles of CHB, and therefore, experiment can use BP and CHB ratio Being worth (BP/CHB) approximatively indicates the ratio between the rate of two kinds of response paths in the HDS reaction of DBT, referred to as hydrogenolysis selectivity.
Catalyst of the present invention is in pressure 7.0MPa, and 300 DEG C of reaction temperature, sulfur content is 850 μ g/g, the grain of catalyst Diameter be 0.25mm under conditions of have good hydrodesulfurization reaction performance, sulfide conversion ratio and hydrogenolysis selectivity compared with It is high.
Detailed description of the invention
Fig. 1 is (NH prepared by the present invention4)4[(HPO3)2Mo5O15]、Ni(NH4)2[(HPO3)2Mo5O15] and Ni2[(HPO3)2Mo5O15] heteropoly acid presoma IR figure；
Fig. 2 is (NH prepared by the present invention4)4[(HPO3)2Mo5O15]、Ni(NH4)2[(HPO3)2Mo5O15] and Ni2[(HPO3)2Mo5O15] heteropoly acid presoma XRD diagram；
Fig. 3 is the XRD diagram of Hydrobon catalyst prepared by the present invention and reference catalyst；
Fig. 4 is nitrogen adsorption-desorption isotherm that the present invention prepares catalyst and reference catalyst；
Fig. 5 is the graph of pore diameter distribution that the present invention prepares catalyst and reference catalyst；
Fig. 6 is the DRIFT spectrogram of catalyst prepared by the present invention and reference catalyst；
Fig. 7 is the high resolution TEM photo that the present invention prepares catalyst and reference catalyst；
Fig. 8 DBT prepares the hydrodesulfurization reaction network on catalyst in the present invention.
Specific embodiment
Below by way of specific experiment example, detailed description of the preferred embodiments, tool described herein Body embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Embodiment 1
NiMoS/γ-Al2O3The preparation method of catalyst, comprises the following processes:
(1) preparation of phosphato-molybdic heteropolyacid presoma.It is dissolved in 70mL water using 4.1g phosphorous acid, 7mL concentration is then added Solution is heated to boiling by the ammonium hydroxide of 15mol/L.It is a small amount of into solution that 14.4g MoO is repeatedly added3(100mmol), powder dissolution After filter.Filtrate boils evaporation and is allowed to volume concentration to 15-20mL, then cools to room temperature.Powdered crystal is collected by filtration, adopts It is dried in air to get heteropoly acid (NH after repeatedly being washed with 10mL ice water4)4[(HPO3)2Mo5O15] (abbreviation P2Mo5)。
(2) preparation of nickeliferous heteropoly acid presoma.To H3PMo12O40Suitable Ba (OH) is added in solution2Make its it is lucky in With obtain Ba3/2PMo12O40Then solution compares according to metering to Ba3/2PMo12O40The sulphur of a certain amount of promoter metal is added in solution Hydrochlorate NiSO4, the BaSO that will be generated in solution4Precipitating is filtered to remove, a certain amount of according to stoichiometric ratio addition in filtrate (NH4)4[(HPO3)2Mo5O15].The solution system is heated to 60 DEG C and continues to be cooled to room temperature after stirring 4h, generation (NH4)3PMo12O40It will form Precipitation, filtering since solubility is very low.The solution is evaporated to obtain the powdered Ni of crude product (NH4)2[(HPO3)2Mo5O15] and Ni2[(HPO3)2Mo5O15] (abbreviation NiP2Mo5Or Ni2P2Mo5), recrystallization three times, obtains pure Product.The application is prepared the metal salt of heteropoly acid by the method for ion exchange by the ammonium salt of heteropoly acid by ion exchange.
(3) preparation of catalyst.By suitable NiP2Mo5Or Ni2P2Mo5Heteropoly acid is configured to maceration extract, using isometric Impregnation is in carrier γ-Al2O3On, it is put into 120 DEG C of baking ovens dry 2h, obtains catalyst precursor.Finally, by catalyst Presoma is placed in presulfurization in tube furnace.Vulcanisation operation is as follows: being passed through N2Atmosphere purges 30min, by N2Atmosphere is switched to H2S/H2 (V/V, 1:9) is warming up to 400 DEG C with 4 DEG C/min, maintains 4h.
Embodiment 2
For catalyst preparation process with embodiment 1, difference is to prepare promoter metal salt used in catalyst precursor to be CoSO4, obtained presoma is Co-Mo-P heteropoly acid, and gained catalyst is CoMoS/ γ-Al2O3。
Embodiment 3
Catalyst preparation process is with embodiment 1, difference nickeliferous heteropoly acid presoma dipping when being prepared catalyst Liquid concentration changes, and catalyst n iMoS active component content is 5wt% (with MoO3It calculates).
Embodiment 4
Catalyst preparation process is with embodiment 1, difference nickeliferous heteropoly acid presoma dipping when being prepared catalyst Liquid concentration changes, and catalyst n iMoS active component content is 12wt% (with MoO3It calculates).
Embodiment 5
Catalyst preparation process is with embodiment 1, difference nickeliferous heteropoly acid presoma dipping when being prepared catalyst Liquid concentration changes, and catalyst n iMoS active component content is 20wt% (with MoO3It calculates).
Embodiment 6
Catalyst preparation process is with embodiment 2, and the presoma of heteropoly acid containing cobalt impregnates when difference is prepared catalyst Liquid concentration changes, and catalyst CoMoS active component content 12wt% is (with MoO3It calculates).
Embodiment 7
Catalyst preparation process uses heteropoly acid precursor construction type not by step (2) with embodiment 1, difference It is confined to (the NH of Strandberg4)4[(HPO3)2Mo5O15], it can also be (the NH of Dawson structure4)6[P2Mo18O62]、 (the NH of Anderson structure4)4[NiMo6O24H6]。
Embodiment 8
Catalyst preparation process uses heteropoly acid precursor construction type not by step (2) with embodiment 2, difference It is confined to (the NH of Strandberg4)4[(HPO3)2Mo5O15], it can also be (the NH of Dawson structure4)6[P2Mo18O62]、 (the NH of Anderson structure4)4[CoMo6O24H6]。
Comparative example 1
Conventional presoma (ammonium molybdate, nickel nitrate and phosphoric acid) and Strandberg structure Ni-Mo-P heteropoly acid is respectively adopted For precursor preparation γ-Al2O3For load same metal load capacity (with MoO3Content be 12wt% calculate) NiMoS/ γ-Al2O3Hydrobon catalyst evaluates its hydrodesulfurization performance respectively.
Catalyst HDS performance test
100mL autoclave is added in the decahydronaphthalene solution (sulfur content is 850 μ g/g) of 1g catalyst and 60mL DBT In, reaction temperature is 300 DEG C, is passed through H2, stagnation pressure 7Mpa continuously stirs 4h.Catalyst particle size is 0.25mm, reactor stirring Speed is 1000rpm, the results are shown in Table 1.
Table 1 is the hydrogenation activity and hydrogenolysis selectivity that the present invention prepares catalyst
Table 1 is it can be seen that product distribution situation after reacted, and CHB and BP are the primary products of reaction, in addition, there are also few The 4H-DBT and 6H-DBT of amount, BP/CHB value is relatively high in the product after reaction, this illustrates that catalyst HDS process compares tendency BP is generated in DDS reaction path.After increasing Ni/Mo atomic ratio, the selectivity of CHB is all improved in reaction product.
As can be seen from Table 1, heteropoly acid NiP2Mo5And Ni2P2Mo5For the conversion of the catalyst DBT of precursor process preparation Rate is respectively 70.5% and 87.9%, hence it is evident that higher than the 52.2% and 60.1% of the catalyst of traditional maceration extract method preparation, is compared The catalyst of conventional precursor preparation, the catalyst based on Strandberg structure Ni-Mo-P heteropoly acid cluster presoma add hydrogen It is desulphurizing activated higher.Table 3 is it can also be seen that the product distribution situation that four kinds of different catalysts obtain.CHB and BP is the master of reaction Product is wanted, in addition, there are also a small amount of 4H-DBT and 6H-DBT.Catalyst is different, and the ratio of BP and CHB is not yet in reaction product Together.Prepared catalyst NiP of the present invention2Mo5/Al2O3、Ni2P2Mo5/Al2O3Compared to reference catalyst RefNiP2Mo5With RefNi2P2Mo5, CHB content is more in product, and BP/CHB ratio is lower.This explanation, the catalyst phase with conventional precursor preparation Than the HDS catalyst based on Strandberg structure nickel molybdenum heteropolyacid cluster presoma is more likely to carry out HYD reaction path, adds Hydrogen desulfuration selectivity is more preferable.Experiment also calculates the pseudo- first-rate reaction constant (k of four kinds of catalystDBT, unit g-1 cat s-1), as can be seen from the table, NiP2Mo5And Ni2P2Mo5For the k of the catalyst of precursor preparationDBTBe apparently higher than other two Kind reference catalyst, it is higher that this also indicates that the HDS catalyst based on Strandberg structure nickel molybdenum heteropolyacid cluster presoma has Catalytic activity.Prepared catalyst of the present invention is reacted for diesel hydrogenation for removal sulphur, has optimal Hydrogenation.
Catalyst structure characterization
(1) by the NiP of synthesis in Fig. 12Mo5、Ni2P2Mo5With raw material P2Mo5Infrared spectrum comparison is carried out, three is basic Similar, Mo=O key stretching vibration peak and Mo-O-Mo bond bending vibration peak position are all very identical.Compared to P2Mo5, NiP2Mo5、 Ni2P2Mo5Infrared spectroscopy in, 1430cm-1Place belongs to the peak and 3180cm of H-N-H-1The peak that place belongs to N-H key weakens, even It disappears；Meanwhile small variation also has occurred in the position of several other infrared absorption peaks.This shows NH4 +By Ni2+Replace, Ni2 +Interaction force between terminal oxygen atoms can be such that other keys are distorted, and cause infrared vibration peak position to occur small inclined It moves, also indirect proof experiment synthesis has obtained NiP for this2Mo5And Ni2P2Mo5。
NiP in Fig. 22Mo5、Ni2P2Mo5The XRD and raw material P of heteropoly acid presoma2Mo5Comparison, some diffraction maximum positions There is biggish offset, this should be due to NH4 +By Ni2+Replace, Ni2+Interaction force meeting between terminal oxygen atoms So that its lattice is changed, the position of some diffraction maximums is caused to change.
NiP is determined by XRF analysis2Mo5And Ni2P2Mo5Atom composition, if the following table 2 is shown.
Table 2 is the XRF elemental analysis result that the present invention prepares catalyst precursor
It as shown in Table 2, is respectively 0.2 and 0.4 with the Ni/Mo atomic ratio that XRF is measured, this and molecular formula NiP2Mo5With Ni2P2Mo5In Ni/Mo atomic ratio be consistent.
In summary NiP has been prepared in several characterization method explanations, ion exchange success, Success in Experiment2Mo5With Ni2P2Mo5Nickel molybdenum heteropolyacid.
(2) as Fig. 3 be catalyst prepared by the present invention and reference catalyst XRD, all samples all 36.8 °, 46.5 ° and 66.3 ° there is wider diffraction maximum, these are all carrier γ-Al2O3Diffraction maximum.In addition, catalyst RefNiP2Mo5And RefNi2P2Mo5It is multiple relatively strong to be that the positions such as 29.3 °, 17.5 °, 11.2 °, 15.2 ° and 8.3 ° occur in 2 θ Diffraction maximum, they correspond respectively to (NH4)4H6NiMo6O24·5H2(211) of O (JCPDS 00-052-0167), (11-1), (100), (10-1) and (010) crystal face.This shows that nickel molybdenum component is agglomerated into phase in above two reference catalyst, dispersion degree compared with Difference, and catalyst n iP2Mo5/Al2O3And Ni2P2Mo5/Al2O3In corresponding position but without there is (NH4)4H6NiMo6O24· 5H2The diffraction maximum of O, this shows in catalyst preparation process, based on Strandberg structure nickel molybdenum heteropolyacid cluster presoma Preferably, crystal grain of the nickel molybdenum component with unformed or size less than 4nm exists HDS catalyst surface nickel molybdenum component dispersibility.
If Fig. 4 is catalyst prepared by the present invention and corresponding reference catalyst and carrier γ-Al2O3N2Adsorption desorption Thermoisopleth, according to IUPAC classification standard, the absorption isotherm of these samples belongs to typical IV type curve, shows their hole Structure is based on mesoporous.
(3) if Fig. 5 and table 3 are respectively catalyst prepared by the present invention and reference catalyst and carrier γ-Al2O3Hole Diameter distribution map and pore property (BET specific surface area, Kong Rong and aperture).
Table 3 is the pore property that the present invention prepares catalyst and reference catalyst.
Fig. 5 and table 3 are as can be seen that with carrier γ-Al2O3It compares, BET specific surface area, Kong Rong and the aperture of four kinds of catalyst There is reduction.This is because after carried metal component, carrier γ-Al2O3Cell channels unavoidably be blocked caused by.Carefully These numbers are analyzed it has been found that compared to carrier γ-Al2O3, NiP2Mo5/Al2O3、Ni2P2Mo5/Al2O3And corresponding reference is urged Agent RefNiP2Mo5、RefNi2P2Mo5BET specific surface area, Kong Rong and aperture respectively reduced 24.0,24.7 and 3.6%, 28.7,28.8 and 6.0%, 31.1,28.8 and 7.2%, 37.3,35.6 and 10.8%.Compared with BET analysis result, do not roast The Catalyst Pore Structure Parameters reduced value of burning be significantly more than roast after catalyst, this is because roasting after bulky grain (NH4)4 [Ni(OH)6Mo6O18]·5H2The MoO of O formation smaller particle3, plug-hole phenomenon, which slows down, causes catalyst pore structure to improve.Compare this A little numbers are it has been found that NiP2Mo5/Al2O3And Ni2P2Mo5/Al2O3Pore structure parameter decreasing value be significantly lower than their corresponding references Catalyst shows its pore structure better than reference catalyst.This is because containing the (NH of larger particles in reference catalyst4)4[Ni (OH)6Mo6O18]·5H2O makes carrier γ-Al2O3In duct block the more serious pore structure so as to cause the catalyst and reduce It is larger.In contrast, NiP2Mo5/Al2O3、Ni2P2Mo5/Al2O3In nickel molybdenum component particle it is smaller, will not significantly reduce and urge The pore structure parameter of agent.More developed pore structure can provide more reacting environment to reaction system and therefore be based on The HDS catalyst of Strandberg structure nickel molybdenum heteropolyacid cluster presoma is more advantageous to the generation of catalysis reaction.
(4) the DRIFT spectrogram of catalyst prepared by the present invention and reference catalyst is given in Fig. 6.It can be seen that four kinds Catalyst is in 2090 and 2062cm-1Nearby all there are two apparent CO absorption peaks, but peak intensity difference is larger.2090cm-1Around The absorption peak of appearance is the MoS of not promoter effect2The CO stretching vibration peak of phase；And 2062cm-1Around the absorption peak of appearance is There is the MoS of promoter effect2The CO stretching vibration peak of phase (Ni-Mo-S active sites).For NiP2Mo5/Al2O3And Ni2P2Mo5/ Al2O3Catalyst, 2062cm-1The absorption peak strength (Ni-Mo-S active sites) at place is apparently higher than the corresponding reference of each and urges Agent.This shows that the HDS catalyst surface based on Strandberg structure nickel molybdenum heteropolyacid cluster presoma contains more Ni- Mo-S active sites, catalytic activity are higher.
(5) Fig. 7 gives the present invention and prepares catalyst and reference catalyst several representational HRTEM photos.It is overall For, the MoS of the catalyst surface after these vulcanizations2It is 3-4 layers that druse, which accumulates the number of plies, and length 3-5nm, they are in catalyst Dispersion on surface is preferable.For quantitative analysis and compare MoS on catalyst2Druse layer length L and accumulation number of plies N, this research pair The different parts of every group of catalyst shoot about 20 HRTEM photos, therefrom choose about 500 MoS2Druse carries out statistics credit Analysis, and calculate MoS2The average platelet length of druseAnd the average stacking number of plies
NiP2Mo5/Al2O3The MoS of catalyst2Druse chip distribution of lengths: less than 2nm is 16.7%, 2-4nm 72%, 4-6nm is 11.3%；And its reference catalyst RefNiP2Mo5MoS2Druse chip distribution of lengths: less than 2nm is 9.5%, 2- 4nm is 59%, 4-6nm 30.3%, 6-8nm 1.2%.Ni2P2Mo5/Al2O3The MoS of catalyst2Druse chip length point Cloth: less than 2nm is 28.6%, 2-4nm 66.1%, 4-6nm 5.2%, 6-8nm 0.1%；And its reference catalyst RefNi2P2Mo5MoS2Druse chip distribution of lengths: less than 2nm is 11.6%, 2-4nm 67%, 4-6nm 21%, 6- 8nm is 0.4%.NiP2Mo5/Al2O3With Ni2P2Mo5/Al2O3Chip length is less than the MoS of 4nm in catalyst2Druse ratio compared with Its reference catalyst is obviously high.
NiP2Mo5/Al2O3The MoS of catalyst2Druse accumulates number of plies distribution: single layer 0.3%, and 2 layers are 18.5%, and 3 layers are 42.6%, 4 layers are 28.4%, and 5 layers are 7.2%, 6 layers and the above are 3%；And its reference catalyst RefNiP2Mo5MoS2It is brilliant Cluster accumulate the number of plies distribution: single layer 0%, 2 layers be 14.5%, 3 layers be 25.1%, 4 layers be 29.7%, 5 layers be 19.8%, 6 layers And the above are 10.9%.Ni2P2Mo5/Al2O3The MoS of catalyst2Druse is accumulated the number of plies and is distributed: single layer 2.8%, and 2 layer 37.6%, 3 Layer 35%, 4 layer 16.7%, 5 layer 5.7%, 6 layers and the above are 2.2%；And its reference catalyst RefNi2P2Mo5MoS2Druse Accumulate the number of plies distribution: single layer 0.1%, 2 layers be 18.5%, 3 layers be 29.1%, 4 layers be 28.4%, 5 layers be 12.2%, 6 layers And the above are 11.7%.NiP2Mo5/Al2O3With Ni2P2Mo5/Al2O3Single layer MoS in catalyst2Druse ratio is catalyzed compared with its reference Agent is high.
The average length of the average MoS2 druse for the various catalyst being calculated according to these dataAnd stack layer NumberAs shown in table 4.
Table 4 is that the present invention prepares the average length of MoS2 druse and the stacking number of plies in catalyst and reference catalyst
As can be seen from Table 4, the NiP after vulcanization2Mo5/Al2O3With Ni2P2Mo5/Al2O3The respective ginseng of catalyst and they It is compared than catalyst, the average tap number of plies (3.3vs.3.9,2.9vs.3.7) and length (3.5vs.4.5nm, 3.2vs.3.8nm) There is reduction.This shows using MoS in the catalyst that Strandberg structure nickel molybdenum heteropolyacid cluster is presoma2Active phase dispersion Du Genggao.
Specific embodiment given by the present invention is rather than to limit model of the invention to be explained further the present invention It encloses.Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to the scope of the present invention Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art do not need Make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.

Claims (6)

1. a kind of preparation method of Hydrobon catalyst, which comprises the following steps:
(1) preparation of metal heteropoly acid presoma
To H3PMo12O40Suitable Ba (OH) is added in solution2It neutralizes it just and obtains Ba3/2PMo12O40Solution, then according to Ratio is measured to Ba3/2PMo12O40The sulfate of a certain amount of promoter metal is added in solution, the BaSO that will be generated in solution4It precipitated It filters out；A certain amount of ammonium salt heteropoly acid presoma is added according to stoichiometric ratio in filtrate, which is heated to It 40 ~ 100 DEG C and is cooled to room temperature after continuing 1 ~ 5 h of stirring, filters (NH4)3PMo12O40, evaporate the solution to obtain crude product Metal heteropoly acid presoma, is finally recrystallized；
(2) preparation of catalyst precursor
Suitable metal heteropoly acid presoma is configured to the maceration extract of various concentration, is impregnated in using equi-volume impregnating Carrierγ-Al2O3On, drying；
(3) catalyst precursor is placed in presulfurization in tube furnace；
Ammonium salt heteropoly acid presoma described in step (1) is (NH4)4[(HPO3)2Mo5O15]、(NH4)6[P2Mo18O62]、 (NH4)4 [NiMo6O24H6One of]；
The sulfate that step (1) is added is CoSO4Or NiSO4；The metal heteropoly acid presoma is the cobalt salt or nickel of heteropoly acid Salt；
(the NH4)4[(HPO3)2Mo5O15] the preparation method comprises the following steps: it is soluble in water using phosphorous acid, a certain amount of ammonium hydroxide is then added, Solution is heated to boiling；It is a small amount of into solution that MoO is repeatedly added3, filtered after powder dissolution；Filtrate boils evaporation, and to be allowed to volume dense It is reduced to certain volume, is then cooled to room temperature；Powdered crystal is collected by filtration, in air after repeatedly washing using 10 mL ice water Middle drying is to get (NH4)4[(HPO3)2Mo5O15]。
2. the preparation method of Hydrobon catalyst according to claim 1, it is characterised in that: the phosphorous acid: ammonium hydroxide: MoO3Between molar ratio be 1:1 ~ 3.1:1.5 ~ 4.
3. the preparation method of Hydrobon catalyst according to claim 1, it is characterised in that: the filtrate boils steaming Hair is allowed to volume concentration to 15-20 mL.
4. using NiMoS or CoMoS as the multicomponent catalyst of active component as made from preparation method described in claim 1.
5. catalyst according to claim 4, it is characterised in that: mass fraction of the catalyst containing active component is 5- 20%, with MoO3Content calculates.
6. application of the catalyst described in claim 4 in diesel hydrogenation for removal sulphur.
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